Andreas Roodt

Bio: Andreas Roodt is an academic researcher from University of the Free State. The author has contributed to research in topics: Crystal structure & Denticity. The author has an hindex of 33, co-authored 320 publications receiving 3437 citations. Previous affiliations of Andreas Roodt include Rand Afrikaans University.

Tuning the Reactivity in Classic Low-Spin d6 Rhenium(I) Tricarbonyl Radiopharmaceutical Synthon by Selective Bidentate Ligand Variation (L,L′-Bid; L,L′= N,N′, N,O, and O,O′ Donor Atom Sets) in fac-[Re(CO)3(L,L′-Bid)(MeOH)]n Complexes

Abstract: A range of fac-[Re(CO)3(L,L′-Bid)(H2O)]n (L,L′-Bid = neutral or monoanionic bidentate ligands with varied L,L′ donor atoms, N,N′, N,O, or O,O′: 1,10-phenanthroline, 2,2′-bipydine, 2-picolinate, 2-quinolinate, 2,4-dipicolinate, 2,4-diquinolinate, tribromotropolonate, and hydroxyflavonate; n = 0, +1) has been synthesized and the aqua/methanol substitution has been investigated. The complexes were characterized by UV–vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Re(CO)3(Phen)(H2O)]NO3·0.5Phen, fac-[Re(CO)3(2,4-dQuinH)(H2O)]·H2O, fac-[Re(CO)3(2,4-dQuinH)Py]Py, and fac-[Re(CO)3(Flav)(CH3OH)]·CH3OH are reported. A four order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N′-Bid) < (N,O-Bid) < (O,O′-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k1, M–1 s–1; k–1, s–1; K1, M–1) for bromide anions as entering nucleophile are as follows: fac-[R...

Steric vs. electronic anomaly observed from iodomethane oxidative addition to tertiary phosphine modified rhodium(I) acetylacetonato complexes following progressive phenyl replacement by cyclohexyl [PR3 = PPh3, PPh2Cy, PPhCy2 and PCy3]

Abstract: Rhodium(I) acetylacetonato complexes of the formula [Rh(acac)(CO)(PR3)] [acac = acetylacetonate, PR3 = PPh31, PCyPh22, PCy2Ph 3, PCy34] were synthesized and the iodomethane oxidative addition to these complexes were studied. Spectroscopic and low temperature (100 K) single crystal X-ray crystallographic data of the rhodium complexes (1–4) indicate a systematic increase in both steric and electronic parameters of the phosphine ligands as phenyl groups on the tertiary phosphine are progressively replaced by cyclohexyl groups in the series. Second order rate constants for the alkyl formation in the oxidative addition of iodomethane in dichloromethane at 25 °C vary with approximately one order-of-magnitude from 6.98(6) × 10−3 M−1s−1 (PCyPh22) to 55(1) × 10−3 M−1 s−1 (PCy2Ph 3) and do not follow the expected electronic pattern from 1 to 4, which indicates a flexibility of the cyclohexyl group, significantly influencing the reactivity. Activation parameters for the reactions range from 35(3) to 44(1) kJ mol−1 for ΔH≠ and −140(5) to −154(9) J K−1 mol−1 for ΔS≠, and are supporting evidence for an associative activation for the oxidative addition step.

I and i

Abstract: There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality. Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Abstract: : The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Transformation of Carbon Dioxide with Homogeneous Transition-Metal Catalysts: A Molecular Solution to a Global Challenge?

Abstract: A plethora of methods have been developed over the years so that carbon dioxide can be used as a reactant in organic synthesis. Given the abundance of this compound, its utilization in synthetic chemistry, particularly on an industrial scale, is still at a rather low level. In the last 35 years, considerable research has been performed to find catalytic routes to transform CO(2) into carboxylic acids, esters, lactones, and polymers in an economic way. This Review presents an overview of the available homogeneous catalytic routes that use carbon dioxide as a C(1) carbon source for the synthesis of industrial products as well as fine chemicals.

The Rich Stereochemistry of Eight‐Vertex Polyhedra: A Continuous Shape Measures Study

Abstract: A stereochemical study of polyhedral eight-vertex structures is presented, based on continuous shape measures (CShM). Reference polyhedra, shape maps, and minimal-distortion interconversion paths are presented for eight-vertex polyhedral and polygonal structures within the CShM framework. The application of these stereochemical tools is analyzed for several families of experimental structures: 1) coordination polyhedra of molecular transition-metal coordination compounds, classified by electron configuration and ligands; 2) edge-bonded polyhedra, including cubane structures, realgar, and metal clusters; 3) octanuclear transition-metal supramolecular architectures; and 4) coordination polyhedra in extended structures in inorganic solids. Structural classification is shown to be greatly facilitated by these tools, and the detection of less common structures, such as the gyrobifastigium, is straightforward.